WO2024103548A1 - Treatment method for used lithium battery leachate - Google Patents

Treatment method for used lithium battery leachate Download PDF

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Publication number
WO2024103548A1
WO2024103548A1 PCT/CN2023/075691 CN2023075691W WO2024103548A1 WO 2024103548 A1 WO2024103548 A1 WO 2024103548A1 CN 2023075691 W CN2023075691 W CN 2023075691W WO 2024103548 A1 WO2024103548 A1 WO 2024103548A1
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liquid
phosphate
solution
precipitation
iron
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PCT/CN2023/075691
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French (fr)
Chinese (zh)
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何然
刘勇奇
张荣荣
鲁游
李长东
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广东邦普循环科技有限公司
湖南邦普循环科技有限公司
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Publication of WO2024103548A1 publication Critical patent/WO2024103548A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B21/00—Obtaining aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the invention relates to the technical field of waste lithium battery recycling, and in particular to a method for treating waste lithium battery leachate.
  • solid waste as a major source of environmental pollution, not only directly pollutes the environment, but also often pollutes through media such as water, air, and soil.
  • Conventional treatment methods such as landfill and incineration will occupy a large amount of land and also cause secondary pollution. Every year, a large amount of solid waste is piled up and cannot be processed, causing a vicious cycle. Solid waste is often called a resource placed in the wrong place. If the materials and energy in it can be effectively recycled and utilized, that is, solid waste can be turned into a resource, it will effectively alleviate this situation and create a certain amount of wealth value.
  • calcium salt is added to remove phosphorus to obtain calcium phosphate.
  • the obtained calcium phosphate also contains about 1% lithium, which is generally scrapped as solid waste, which is a huge waste of lithium resources and also causes serious pollution to the environment.
  • the object of the present invention is to provide a method for treating waste lithium battery leachate, aiming at effectively recovering lithium in calcium phosphate slag.
  • the present invention is achieved in that:
  • the present invention provides a method for treating waste lithium battery leachate, comprising sequentially performing copper removal, iron and aluminum removal, nickel, cobalt and manganese precipitation, primary lithium precipitation, secondary lithium precipitation and phosphorus removal;
  • phosphorus removal is to add excess calcium salt to the liquid after secondary lithium precipitation, and calcium phosphate and wastewater are obtained after solid-liquid separation. Iron and aluminum removal is carried out using calcium phosphate.
  • it includes:
  • Copper removal Add metal elements to the waste lithium battery leachate for replacement, and obtain elemental copper and copper after copper removal after solid-liquid separation. liquid;
  • Iron and aluminum removal calcium phosphate is added to the copper removal solution, and iron and aluminum slag and iron and aluminum removal solution are obtained after solid-liquid separation; in the process of iron and aluminum removal, the molar ratio of the amount of calcium phosphate added to the total amount of iron and aluminum in the copper removal solution is controlled to be 0.8-1.1:1;
  • Precipitating nickel, cobalt and manganese adding alkaline solution to the liquid after iron and aluminum removal, and obtaining nickel, cobalt and manganese hydroxide and the liquid after nickel, cobalt and manganese precipitation after solid-liquid separation;
  • Primary lithium precipitation adding carbonate to the solution after nickel, cobalt and manganese precipitation, and obtaining lithium carbonate and the solution after primary lithium precipitation after solid-liquid separation;
  • Secondary lithium precipitation adding phosphate to the liquid after primary lithium precipitation, and obtaining lithium phosphate and liquid after secondary lithium precipitation after solid-liquid separation;
  • Phosphorus removal Add excess calcium salt to the liquid after secondary lithium precipitation, and obtain calcium phosphate and qualified wastewater after solid-liquid separation.
  • the metal element is selected from at least one of manganese powder, iron powder and aluminum powder, the replacement reaction time is 0.5-3h, and the reaction temperature is 60-90°C;
  • the molar ratio of the added amount of the metal element to the copper content in the waste lithium battery leachate is 1.05 to 1.2:1.
  • the iron and aluminum removal includes: heating the copper-removed solution to 80-95° C., adding an oxidant and calcium phosphate, reacting for 20-60 minutes, and separating the solid from the liquid;
  • the liquid-to-solid ratio is controlled to be 0-10;
  • the obtained iron-aluminum slag is washed, and the liquid-to-solid mass ratio is controlled to be 3-10:1 during washing.
  • the oxidant is selected from at least one of sodium chlorate, potassium chlorate, manganese dioxide and hydrogen peroxide, and the molar amount of the oxidant added is 1 to 1.5 times the theoretical amount of ferrous iron in the solution after oxidation and copper removal.
  • the process of precipitating nickel, cobalt and manganese includes: heating the liquid after iron and aluminum removal to 50-95° C., adding an alkaline solution to react for 0.5-3 hours, and separating the solid and liquid; the amount of the alkaline solution added is to control the molar ratio of hydroxide to the total amount of nickel, cobalt and manganese to be 2.05-2.5:1;
  • the alkaline solution added during the precipitation of nickel, cobalt and manganese is selected from at least one of sodium hydroxide solution, potassium hydroxide solution and ammonia water, and the mass fraction of the alkaline solution is 25-35%.
  • the process of primary lithium precipitation includes: heating the solution after nickel, cobalt and manganese precipitation to 80-95° C., adding a carbonate solution to react for 0.5-3 hours, and separating the solid from the liquid;
  • the amount of carbonate added is to control the molar ratio of carbonate ions to lithium ion content in the solution after nickel, cobalt and manganese precipitation to be 0.5 to 5:1;
  • the carbonate is selected from at least one of sodium carbonate, potassium carbonate and ammonium carbonate, and the mass fraction of the carbonate solution is 10-20%.
  • the process of secondary lithium precipitation includes: adding a phosphate solution to the liquid after the primary lithium precipitation for a reaction of 0.5-3h, solid-liquid separation, and controlling the reaction temperature to 20-80°C;
  • the amount of phosphate added is to control the molar ratio of the amount of phosphate ions to the content of lithium ions in the solution after the first lithium precipitation. 0.3 ⁇ 5:1;
  • the phosphate is selected from at least one of sodium phosphate, potassium phosphate, ammonium phosphate, ammonium hydrogen phosphate and ammonium dihydrogen phosphate, and the mass fraction of the phosphate solution is 10-20%.
  • the phosphorus removal process includes: adding excess calcium salt to the secondary lithium precipitation solution for a reaction of 0.5-3h, solid-liquid separation, and controlling the reaction temperature to 20-80°C;
  • the amount of calcium salt added is to control the molar ratio of calcium to phosphate in the solution after secondary lithium precipitation to be 0.6 to 5:1.
  • the calcium salt is selected from at least one of calcium oxide, calcium hydroxide and calcium sulfate;
  • the calcium salt is added in the form of slurry, and the mass fraction of the calcium salt is 10-20%.
  • the invention has the following beneficial effects: during phosphorus removal, excessive calcium salt reaction is utilized to make the obtained calcium phosphate slag alkaline, and excessive calcium hydroxide in the calcium phosphate is utilized to replace the traditional alkali for adjusting the pH value, so that the calcium phosphate slag is effectively utilized, the resource utilization of calcium phosphate is realized, and the valuable metal lithium in the calcium phosphate is recovered; the intermediate products of iron-aluminum slag and nickel-cobalt-manganese hydroxide slag have low impurity contents, which reduces the production cost of the entire process and improves the economic benefits.
  • FIG. 1 is a process flow chart of a treatment method provided in an embodiment of the present invention.
  • the embodiment of the present invention provides a method for treating waste lithium battery leachate, referring to FIG. 1 , comprising the following steps:
  • the solid-liquid separation method is not limited, and a common filtering method can be used.
  • the metal element is selected from at least one of manganese powder, iron powder and aluminum powder. Since manganese exists in the leaching solution, the use of metal elements such as manganese powder will not introduce impurities.
  • the replacement reaction time is 0.5-3h
  • the reaction temperature is 60-90°C.
  • the reaction temperature can be 60°C, 70°C, 80°C, 90°C, etc.
  • the reaction time can be 0.5h, 1.0h, 1.5h, 2.0h, 2.5h, 3.0h, etc.
  • the molar ratio of the amount of metal element added to the copper content in the waste lithium battery leachate is 1.05-1.2:1 (such as 1.05:1, 1.10:1, 1.15:1, 1.20:1, etc.). Controlling within this range can more fully replace copper. After testing, the pH value of the liquid after copper removal is 1.5-2.0.
  • Iron and aluminum are removed by using calcium phosphate, which replaces the traditional alkali for adjusting pH value. It will not introduce impure metals, reduces production costs, and improves economic benefits. More importantly, it can recycle calcium phosphate solid waste and recover the valuable metal lithium in calcium phosphate.
  • iron and aluminum are removed by adding calcium phosphate to the copper removal liquid, and iron-aluminum slag and iron-aluminum removal liquid are obtained after solid-liquid separation; in the process of iron and aluminum removal, the molar ratio of the amount of calcium phosphate added to the total amount of iron and aluminum in the copper removal liquid is controlled to be 0.8-1.1:1 (such as 0.8:1, 0.9:1, 1.0:1, 1.1:1, etc.).
  • the amount of calcium phosphate added By precisely controlling the amount of calcium phosphate added, the iron and aluminum can be fully deposited, and the introduction of too much phosphorus element is avoided, which will not cause the problem of excessive phosphorus impurity content in the intermediate product.
  • the iron and aluminum removal includes: heating the copper-removed solution to 80-95°C, adding an oxidant and calcium phosphate, reacting for 20-60 minutes, separating the solid and the liquid, oxidizing the divalent iron ions in the solution with the oxidant, reacting with the calcium phosphate and depositing them, and the calcium ions combine with the sulfate ions in the solution and deposit them.
  • the heating temperature can be 80°C, 85°C, 90°C, 95°C, etc.
  • the reaction time can be 20 min, 30 min, 40 min, 50 min, 60 min, etc.
  • the oxidant is selected from at least one of sodium chlorate, potassium chlorate, manganese dioxide and hydrogen peroxide, and the molar amount of the oxidant added is 1 to 1.5 times the theoretical amount of ferrous iron in the solution after copper removal by oxidation.
  • the oxidant can be selected from any one or more of the above raw materials, and the amount of the oxidant is controlled to promote the sufficient deposition of iron and aluminum.
  • the liquid-to-solid ratio is controlled to be 0-10, that is, calcium phosphate can be added in the form of calcium phosphate solution or in the form of dry powder, which reduces the introduction of water, saves water resources, speeds up the reaction process, and improves production efficiency.
  • the liquid-to-solid mass ratio can be 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, etc.
  • the obtained iron-aluminum slag is washed to remove surface impurities, and the liquid-to-solid mass ratio during washing is controlled to be 3-10:1, such as 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, etc.
  • the pH value of the liquid after iron and aluminum removal is 2.0-5.0
  • the content of Ni, Co, Mn, and Li in the iron and aluminum slag is not higher than 0.01%
  • the P content of the liquid after iron and aluminum removal is less than 0.1g/L.
  • the low phosphorus content of the liquid after iron and aluminum removal reduces the cost of water treatment; reduces the amount of valuable metals entrained in the iron and aluminum slag, reduces the loss rate of valuable metals, improves production economic benefits, and reduces the environmental impact of harmful metals pollution.
  • Alkaline solution is added to the liquid after iron and aluminum removal, and nickel, cobalt and manganese hydroxide and nickel, cobalt and manganese precipitation liquid are obtained after solid-liquid separation to recover valuable metals such as nickel, cobalt and manganese in the leaching solution.
  • the process of precipitating nickel, cobalt and manganese includes: heating the liquid after iron and aluminum removal to 50-95°C, adding alkaline solution to react for 0.5-3h, and separating the solid and liquid; the amount of alkaline solution added is to control the molar ratio of hydroxide to the total amount of nickel, cobalt and manganese to be 2.05-2.5:1 (such as 2.05:1, 2.10:1, 2.20:1, 2.30:1, 2.40:1, 2.50:1, etc.), so that the nickel, cobalt and manganese elements can be fully deposited.
  • the heating temperature of the liquid after iron and aluminum removal can be 50°C, 60°C, 70°C, 80°C, 90°C, 95°C, etc.
  • the reaction time can be 0.5h, 1.0h, 1.5h, 2.0h, 2.5h, 3.0h, etc.
  • the alkaline solution added during the precipitation of nickel, cobalt and manganese is selected from at least one of sodium hydroxide solution, potassium hydroxide solution and ammonia water, and any of the above alkaline solutions can be used.
  • the mass fraction of the alkaline solution is 25-35%, such as 25%, 30%, 35%, etc.
  • Carbonate is added to the liquid after nickel, cobalt and manganese precipitation, and lithium carbonate and a liquid after primary lithium precipitation are obtained after solid-liquid separation. Most of the lithium in the liquid after nickel, cobalt and manganese precipitation can be precipitated in the form of lithium carbonate, and the high-priced lithium element is recovered.
  • the process of primary lithium precipitation includes: heating the solution after nickel, cobalt and manganese precipitation to 80-95°C, adding carbonate solution to react for 0.5-3h, and separating the solid and liquid; wherein the amount of carbonate added is to control the molar ratio of the amount of carbonate ions to the content of lithium ions in the solution after nickel, cobalt and manganese precipitation to be 0.5-5:1 (such as 0.5:1, 1.0:1, 2.0:1, 3.0:1, 4.0:1, 5.0:1, etc.).
  • the reaction conditions are precisely controlled to allow lithium to be deposited more fully.
  • the heating temperature of the solution after nickel, cobalt and manganese precipitation can be 80°C, 85°C, 90°C, 95°C, etc.
  • the reaction time can be 0.5h, 1.0h, 2.0h, 3.0h, etc.
  • the carbonate is selected from at least one of sodium carbonate, potassium carbonate and ammonium carbonate, and may be any of the above.
  • the mass fraction of the carbonate solution is 10-20%, such as 10%, 15%, 20%, etc.
  • Phosphate is added to the liquid after the first lithium precipitation, and lithium phosphate and the liquid after the second lithium precipitation are obtained after solid-liquid separation.
  • the lithium that is not deposited in the first lithium precipitation process is further removed from the solution through the second lithium precipitation and recovered.
  • the process of secondary lithium precipitation includes: adding phosphate solution to the liquid after primary lithium precipitation for reaction for 0.5-3h, solid-liquid separation, and controlling the reaction temperature to 20-80°C; wherein, the amount of phosphate added is to control the molar ratio of the amount of phosphate ions to the content of lithium ions in the liquid after primary lithium precipitation to be 0.3-5:1 (such as 0.3:1, 1.0:1, 2.0:1, 3.0:1, 4.0:1, 5.0:1, etc.).
  • the reaction conditions of secondary lithium precipitation it is beneficial to fully remove the residual lithium in the solution and obtain full recovery.
  • the reaction temperature can be 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, etc.
  • the reaction time can be 0.5h, 1.0h, 2.0h, 3.0h, etc.
  • the phosphate is selected from at least one of sodium phosphate, potassium phosphate, ammonium phosphate, ammonium hydrogen phosphate and ammonium dihydrogen phosphate, and can be any one or more of the above phosphates.
  • the mass fraction of the phosphate solution is 10-20%, such as 10%, 15%, 20%, etc.
  • Phosphorus removal is done by adding excess calcium salt to the liquid after secondary lithium precipitation, and obtaining calcium phosphate and qualified wastewater after solid-liquid separation.
  • the precipitated calcium phosphate is alkaline and can be used in the process of iron and aluminum removal.
  • the phosphorus removal process includes: adding an excess of calcium salt to the secondary lithium precipitation solution for a reaction of 0.5-3 hours, solid-liquid separation, and controlling the reaction temperature to 20-80°C; wherein the amount of calcium salt added is to control the molar ratio of calcium to phosphate in the secondary lithium precipitation solution to be 0.6-5:1 (such as 0.6:1, 1.0:1, 2.0:1, 3.0:1, 4.0:1, 5.0:1, etc.).
  • the amount of calcium salt added is to control the molar ratio of calcium to phosphate in the secondary lithium precipitation solution to be 0.6-5:1 (such as 0.6:1, 1.0:1, 2.0:1, 3.0:1, 4.0:1, 5.0:1, etc.).
  • the reaction temperature can be 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, etc.
  • the reaction time can be 0.5h, 1.0h, 2.0h, 3.0h, etc.
  • the calcium salt is selected from at least one of calcium oxide, calcium hydroxide and calcium sulfate, and any one or more of the above can be selected.
  • the calcium salt is preferably added in the form of slurry, and the mass fraction of the calcium salt is 10-20%, such as 10%, 15%, 20%, etc.
  • the waste lithium battery material is roasted, and the roasted material is crushed and sorted to obtain battery powder, which is then leached with sulfuric acid to obtain battery leachate.
  • This embodiment provides a method for treating waste lithium battery leachate, comprising the following steps:
  • step (2) The copper-removed solution obtained in step (1) is heated to 90°C, 0.06 g of oxidizing agent sodium chlorate is added and treated with the above leaching solution.
  • the calcium phosphate obtained in the recycling process step (6) is fully stirred, and calcium phosphate is added at a molar ratio of the total molar amount of Fe and Al to the molar amount of calcium phosphate of 1:0.8. After reacting for 30 minutes, it is filtered to obtain iron-aluminum slag and iron-aluminum-removed liquid;
  • step (3) The iron and aluminum-removed liquid obtained in step (2) is heated to 60° C., 0.42 L of a 30% sodium hydroxide solution is added, the mixture is reacted for 2 h, and the nickel, cobalt and manganese hydroxides and the nickel, cobalt and manganese precipitation liquid are obtained by filtration;
  • step (3) The nickel-cobalt-manganese precipitation solution obtained in step (3) is heated to 90° C., 0.63 L of a 15% by mass sodium carbonate solution is added, the reaction is carried out for 2 h, and lithium carbonate and a primary lithium precipitation solution are obtained by filtering;
  • step (4) taking the primary lithium precipitation liquid obtained in step (4), adding 0.26 L of 15% sodium phosphate solution by mass, reacting at room temperature (25° C.) for 2 h, and filtering to obtain lithium phosphate and secondary lithium precipitation liquid;
  • step (6) Take the secondary lithium precipitation liquid obtained in step (5), add 0.058L of calcium oxide slurry with a mass fraction of 15%, react at room temperature (25°C) for 2h, and filter to obtain calcium phosphate and qualified wastewater.
  • Example 1 The only difference from Example 1 is that the amount of calcium phosphate added in step (2) is different.
  • the molar ratio of the total molar amount of Fe and Al to the molar amount of calcium phosphate in Examples 2-8 is 1:1.1, 1:0.85, 1:0.9, 1:1.0, 1:1.05, 1:1.3, and 1:0.5, respectively.
  • Example 1 The only difference from Example 1 is that the reaction temperature of step (2) for removing iron and aluminum is different.
  • the reaction temperatures of Examples 9 to 12 are 40°C, 80°C, 85°C, and 95°C, respectively.
  • the specific method of comparative example 1 refers to Chinese patent CN201811398512.2.
  • Ni of the iron-aluminum slag is 0.5-1.4wt%
  • Co is 0.06-0.5wt%
  • Mn is 0-0.05wt%.
  • the nickel and cobalt contents are both relatively high, resulting in a waste of valuable metals.
  • the lithium recovery rates of Examples 1-6 are all relatively high (lithium recovery rate is greater than 99%), and the content of impurities such as phosphorus in the solution after iron and aluminum removal is very low, and the content of nickel, cobalt, manganese and lithium in the iron-aluminum slag is very low.
  • the molar ratio of calcium phosphate to iron and aluminum in the solution exceeds 0.8-1.1:1, and the impurity content in the solution after iron and aluminum removal and the iron-aluminum slag is very high, which increases the difficulty of subsequent treatment.

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Abstract

The present invention relates to the technical field of used lithium battery recycling. Disclosed is a treatment method for used lithium battery leachate. The treatment method for used lithium battery leachate comprises copper removal, ferro-aluminum removal, nickel-cobalt-manganese precipitation, primary lithium precipitation, secondary lithium precipitation and phosphorus removal which are performed successively. During the phosphorus removal, using an excess of calcium salt in the reaction makes an obtained calcium phosphate residue alkaline, and calcium phosphate replaces an alkali for traditionally adjusting pH values such that the calcium phosphate residue is effectively utilized. Thus, calcium phosphate is used as a resource in order to recycle valuable metal lithium therein. Intermediate products, i.e. a ferro-aluminum residue and a nickel-cobalt-manganese hydroxide residue, each have a relatively low impurity content, thus reducing the production cost of the whole process, and increasing the economic benefit.

Description

一种废旧锂电池浸出液的处理方法A method for treating waste lithium battery leachate 技术领域Technical Field
本发明涉及废旧锂电池回收技术领域，具体而言，涉及一种废旧锂电池浸出液的处理方法。The invention relates to the technical field of waste lithium battery recycling, and in particular to a method for treating waste lithium battery leachate.
背景技术Background technique
随着环境标准的要求愈发严格，固体废物作为环境的一大污染源，不仅仅会直接污染环境，而且常通过媒介，如水、气、土壤等进行污染。常规处理方法如填埋、焚烧等会占据大量的土地同时还会产生二次污染，每年有大量的固体废物堆积无法处理，造成恶性循环。而固体废物常被称为放错地方的资源，如能有效回收利用其中的物质和能源，即实现固体废物资源化，将有效的缓解这一现状并创造一定的财富价值。As environmental standards become increasingly stringent, solid waste, as a major source of environmental pollution, not only directly pollutes the environment, but also often pollutes through media such as water, air, and soil. Conventional treatment methods such as landfill and incineration will occupy a large amount of land and also cause secondary pollution. Every year, a large amount of solid waste is piled up and cannot be processed, causing a vicious cycle. Solid waste is often called a resource placed in the wrong place. If the materials and energy in it can be effectively recycled and utilized, that is, solid waste can be turned into a resource, it will effectively alleviate this situation and create a certain amount of wealth value.
目前，每年有大量地含磷的工业废水和生活污水产生，中和沉淀法因其廉价、快速、操作简单的优点常用于含磷酸盐废水处理，而此种方法往往会带来大量的沉淀物，这些沉淀物常被定性为危险固体废物，因此后续处理难度大、成本高。At present, a large amount of phosphorus-containing industrial wastewater and domestic sewage is generated every year. The neutralization precipitation method is often used for the treatment of phosphate-containing wastewater because of its advantages of being cheap, fast and easy to operate. However, this method often produces a large amount of precipitates, which are often classified as hazardous solid wastes. Therefore, subsequent treatment is difficult and costly.
在废旧锂电池回收锂的过程中，会由于加入钙盐进行除磷，得到磷酸钙。而得到的磷酸钙还含有1％左右的锂，一般都作为固废进行报废，这对锂资源是极大的浪费，并且对环境也有严重的污染。In the process of recycling lithium from waste lithium batteries, calcium salt is added to remove phosphorus to obtain calcium phosphate. The obtained calcium phosphate also contains about 1% lithium, which is generally scrapped as solid waste, which is a huge waste of lithium resources and also causes serious pollution to the environment.
鉴于此，特提出本发明。In view of this, the present invention is proposed.
发明内容Summary of the invention
本发明的目的在于提供一种废旧锂电池浸出液的处理方法，旨在有效回收磷酸钙渣中的锂。The object of the present invention is to provide a method for treating waste lithium battery leachate, aiming at effectively recovering lithium in calcium phosphate slag.
本发明是这样实现的：The present invention is achieved in that:
第一方面，本发明提供一种废旧锂电池浸出液的处理方法，包括依次进行的除铜、除铁铝、沉镍钴锰、一次沉锂、二次沉锂和除磷；In a first aspect, the present invention provides a method for treating waste lithium battery leachate, comprising sequentially performing copper removal, iron and aluminum removal, nickel, cobalt and manganese precipitation, primary lithium precipitation, secondary lithium precipitation and phosphorus removal;
其中，除磷是在二次沉锂后液中加入过量的钙盐，固液分离后得到磷酸钙和废水，除铁铝是利用磷酸钙进行处理。Among them, phosphorus removal is to add excess calcium salt to the liquid after secondary lithium precipitation, and calcium phosphate and wastewater are obtained after solid-liquid separation. Iron and aluminum removal is carried out using calcium phosphate.
在可选的实施方式中，包括：In an optional embodiment, it includes:
除铜：向废旧锂电池浸出液中加入金属单质进行置换，固液分离后得到单质铜和除铜后 液；Copper removal: Add metal elements to the waste lithium battery leachate for replacement, and obtain elemental copper and copper after copper removal after solid-liquid separation. liquid;
除铁铝：向除铜后液中加入磷酸钙，固液分离后得到铁铝渣和除铁铝后液；在除铁铝的过程中，控制磷酸钙的加入量与除铜后液中铁铝总量的摩尔比为0.8-1.1:1；Iron and aluminum removal: calcium phosphate is added to the copper removal solution, and iron and aluminum slag and iron and aluminum removal solution are obtained after solid-liquid separation; in the process of iron and aluminum removal, the molar ratio of the amount of calcium phosphate added to the total amount of iron and aluminum in the copper removal solution is controlled to be 0.8-1.1:1;
沉镍钴锰：向除铁铝后液中加入碱溶液，固液分离后得到氢氧化镍钴锰和沉镍钴锰后液；Precipitating nickel, cobalt and manganese: adding alkaline solution to the liquid after iron and aluminum removal, and obtaining nickel, cobalt and manganese hydroxide and the liquid after nickel, cobalt and manganese precipitation after solid-liquid separation;
一次沉锂：向沉镍钴锰后液中加入碳酸盐，固液分离后得到碳酸锂和一次沉锂后液；Primary lithium precipitation: adding carbonate to the solution after nickel, cobalt and manganese precipitation, and obtaining lithium carbonate and the solution after primary lithium precipitation after solid-liquid separation;
二次沉锂：向一次沉锂后液中加入磷酸盐，固液分离后得到磷酸锂和二次沉锂后液；Secondary lithium precipitation: adding phosphate to the liquid after primary lithium precipitation, and obtaining lithium phosphate and liquid after secondary lithium precipitation after solid-liquid separation;
除磷：向二次沉锂后液中加入过量的钙盐，固液分离后得到磷酸钙和合格废水。Phosphorus removal: Add excess calcium salt to the liquid after secondary lithium precipitation, and obtain calcium phosphate and qualified wastewater after solid-liquid separation.
在可选的实施方式中，金属单质选自锰粉、铁粉和铝粉中的至少一种，置换反应时间为0.5-3h，反应温度为60-90℃；In an optional embodiment, the metal element is selected from at least one of manganese powder, iron powder and aluminum powder, the replacement reaction time is 0.5-3h, and the reaction temperature is 60-90°C;
优选地，金属单质的加入量与废旧锂电池浸出液中铜含量的摩尔比为1.05～1.2：1。Preferably, the molar ratio of the added amount of the metal element to the copper content in the waste lithium battery leachate is 1.05 to 1.2:1.
在可选的实施方式中，除铁铝包括：将除铜后液加热至80-95℃，加入氧化剂和磷酸钙，反应20-60min，固液分离；In an optional embodiment, the iron and aluminum removal includes: heating the copper-removed solution to 80-95° C., adding an oxidant and calcium phosphate, reacting for 20-60 minutes, and separating the solid from the liquid;
优选地，磷酸钙加入时控制液固比为0-10；Preferably, when calcium phosphate is added, the liquid-to-solid ratio is controlled to be 0-10;
优选地，对得到的铁铝渣进行洗涤，洗涤时控制液固质量比为3-10:1。Preferably, the obtained iron-aluminum slag is washed, and the liquid-to-solid mass ratio is controlled to be 3-10:1 during washing.
在可选的实施方式中，氧化剂选自氯酸钠、氯酸钾、二氧化锰和过氧化氢中的至少一种，氧化剂加入的摩尔量是氧化除铜后液中亚铁的理论量的1～1.5倍。In an optional embodiment, the oxidant is selected from at least one of sodium chlorate, potassium chlorate, manganese dioxide and hydrogen peroxide, and the molar amount of the oxidant added is 1 to 1.5 times the theoretical amount of ferrous iron in the solution after oxidation and copper removal.
在可选的实施方式中，沉镍钴锰的过程包括：将除铁铝后液加热至50-95℃，加入碱溶液反应0.5-3h，固液分离；加入的碱溶液的量是控制氢氧根和镍钴锰总量的摩尔比为2.05～2.5：1；In an optional embodiment, the process of precipitating nickel, cobalt and manganese includes: heating the liquid after iron and aluminum removal to 50-95° C., adding an alkaline solution to react for 0.5-3 hours, and separating the solid and liquid; the amount of the alkaline solution added is to control the molar ratio of hydroxide to the total amount of nickel, cobalt and manganese to be 2.05-2.5:1;
优选地，沉镍钴锰的过程中加入的碱溶液选自氢氧化钠溶液、氢氧化钾溶液和氨水中的至少一种，碱溶液的质量分数为25-35％。Preferably, the alkaline solution added during the precipitation of nickel, cobalt and manganese is selected from at least one of sodium hydroxide solution, potassium hydroxide solution and ammonia water, and the mass fraction of the alkaline solution is 25-35%.
在可选的实施方式中，一次沉锂的过程包括：将沉镍钴锰后液加热至80-95℃，加入碳酸盐溶液反应0.5-3h，固液分离；In an optional embodiment, the process of primary lithium precipitation includes: heating the solution after nickel, cobalt and manganese precipitation to 80-95° C., adding a carbonate solution to react for 0.5-3 hours, and separating the solid from the liquid;
其中，碳酸盐的加入量是控制碳酸根离子的量与沉镍钴锰后液中锂离子含量的摩尔比为0.5～5：1；The amount of carbonate added is to control the molar ratio of carbonate ions to lithium ion content in the solution after nickel, cobalt and manganese precipitation to be 0.5 to 5:1;
优选地，碳酸盐选自碳酸钠、碳酸钾和碳酸铵中的至少一种，碳酸盐溶液的质量分数为10-20％。Preferably, the carbonate is selected from at least one of sodium carbonate, potassium carbonate and ammonium carbonate, and the mass fraction of the carbonate solution is 10-20%.
在可选的实施方式中，二次沉锂的过程包括：向一次沉锂后液中加入磷酸盐溶液反应0.5-3h，固液分离，控制反应温度为20-80℃；In an optional embodiment, the process of secondary lithium precipitation includes: adding a phosphate solution to the liquid after the primary lithium precipitation for a reaction of 0.5-3h, solid-liquid separation, and controlling the reaction temperature to 20-80°C;
其中，磷酸盐的加入量是控制磷酸根离子的量与一次沉锂后液中锂离子含量的摩尔比为 0.3～5：1；The amount of phosphate added is to control the molar ratio of the amount of phosphate ions to the content of lithium ions in the solution after the first lithium precipitation. 0.3～5:1;
优选地，磷酸盐选自磷酸钠、磷酸钾、磷酸铵、磷酸氢铵和磷酸二氢铵中的至少一种，磷酸盐溶液的质量分数为10-20％。Preferably, the phosphate is selected from at least one of sodium phosphate, potassium phosphate, ammonium phosphate, ammonium hydrogen phosphate and ammonium dihydrogen phosphate, and the mass fraction of the phosphate solution is 10-20%.
在可选的实施方式中，除磷的过程包括：向二次沉锂后液中加入过量的钙盐反应0.5-3h，固液分离，控制反应温度为20-80℃；In an optional embodiment, the phosphorus removal process includes: adding excess calcium salt to the secondary lithium precipitation solution for a reaction of 0.5-3h, solid-liquid separation, and controlling the reaction temperature to 20-80°C;
其中，钙盐的加入量是控制钙与二次沉锂后液中磷酸根的摩尔比为0.6～5：1。The amount of calcium salt added is to control the molar ratio of calcium to phosphate in the solution after secondary lithium precipitation to be 0.6 to 5:1.
在可选的实施方式中，钙盐选自氧化钙、氢氧化钙和硫酸钙中的至少一种；In an optional embodiment, the calcium salt is selected from at least one of calcium oxide, calcium hydroxide and calcium sulfate;
优选地，钙盐以浆料的形式加入，钙盐的质量分数为10-20％。Preferably, the calcium salt is added in the form of slurry, and the mass fraction of the calcium salt is 10-20%.
本发明具有以下有益效果：在除磷时利用过量的钙盐反应，使得到的磷酸钙渣呈碱性，利用磷酸钙中过量的氢氧化钙替换传统调节pH值的碱，将磷酸钙渣得到有效利用，实现了对磷酸钙的资源化利用，回收磷酸钙中的有价金属锂；中间产品铁铝渣、氢氧化镍钴锰渣杂质含量较低，降低了整个工艺的生产成本，提高了经济效益。The invention has the following beneficial effects: during phosphorus removal, excessive calcium salt reaction is utilized to make the obtained calcium phosphate slag alkaline, and excessive calcium hydroxide in the calcium phosphate is utilized to replace the traditional alkali for adjusting the pH value, so that the calcium phosphate slag is effectively utilized, the resource utilization of calcium phosphate is realized, and the valuable metal lithium in the calcium phosphate is recovered; the intermediate products of iron-aluminum slag and nickel-cobalt-manganese hydroxide slag have low impurity contents, which reduces the production cost of the entire process and improves the economic benefits.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
为了更清楚地说明本发明实施例的技术方案，下面将对实施例中所需要使用的附图作简单地介绍，应当理解，以下附图仅示出了本发明的某些实施例，因此不应被看作是对范围的限定，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他相关的附图。In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for use in the embodiments are briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other related drawings can be obtained based on these drawings without creative work.
图1为本发明实施例提供处理方法的工艺流程图。FIG. 1 is a process flow chart of a treatment method provided in an embodiment of the present invention.
具体实施方式Detailed ways
为使本发明实施例的目的、技术方案和优点更加清楚，下面将对本发明实施例中的技术方案进行清楚、完整地描述。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。In order to make the purpose, technical scheme and advantages of the embodiments of the present invention clearer, the technical scheme in the embodiments of the present invention will be described clearly and completely below. If the specific conditions are not specified in the embodiments, they are carried out according to conventional conditions or conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be purchased commercially.
本发明实施例提供一种废旧锂电池浸出液的处理方法，请参照图1，包括如下步骤：The embodiment of the present invention provides a method for treating waste lithium battery leachate, referring to FIG. 1 , comprising the following steps:
S1、除铜S1. Copper removal
向废旧锂电池浸出液中加入金属单质进行置换，固液分离后得到单质铜和除铜后液，通过置换反应将浸出液中的铜置换出来，得到单质铜。固液分离的方式不限，可以采用常用的过滤的方式。Add a metal element to the waste lithium battery leachate for replacement, obtain elemental copper and copper-removed liquid after solid-liquid separation, and replace the copper in the leachate through a replacement reaction to obtain elemental copper. The solid-liquid separation method is not limited, and a common filtering method can be used.
在一些实施例中，金属单质选自锰粉、铁粉和铝粉中的至少一种，由于浸出液中存在锰，采用锰粉等金属单质不会引入杂质。In some embodiments, the metal element is selected from at least one of manganese powder, iron powder and aluminum powder. Since manganese exists in the leaching solution, the use of metal elements such as manganese powder will not introduce impurities.
在一些实施例中，置换反应时间为0.5-3h，反应温度为60-90℃，通过控制反应温度和时 间以使反应更加充分。具体地，反应温度可以为60℃、70℃、80℃、90℃等，反应时间可以为0.5h、1.0h、1.5h、2.0h、2.5h、3.0h等。In some embodiments, the replacement reaction time is 0.5-3h, and the reaction temperature is 60-90°C. Specifically, the reaction temperature can be 60°C, 70°C, 80°C, 90°C, etc., and the reaction time can be 0.5h, 1.0h, 1.5h, 2.0h, 2.5h, 3.0h, etc.
在一些实施例中，金属单质的加入量与废旧锂电池浸出液中铜含量的摩尔比为1.05～1.2：1(如1.05:1、1.10:1、1.15:1、1.20:1等)，控制在此范围内能够更充分地将铜置换出来，经检测除铜后液pH值为1.5-2.0。In some embodiments, the molar ratio of the amount of metal element added to the copper content in the waste lithium battery leachate is 1.05-1.2:1 (such as 1.05:1, 1.10:1, 1.15:1, 1.20:1, etc.). Controlling within this range can more fully replace copper. After testing, the pH value of the liquid after copper removal is 1.5-2.0.
S2、除铁铝S2, iron and aluminum removal
除铁铝是利用磷酸钙进行处理，代替传统调节pH值的碱，不会引入杂质金属，降低了生产成本，提高了经济效益，更为重要的是能够将磷酸钙固体废料进行资源化利用，回收磷酸钙中的有价金属锂。Iron and aluminum are removed by using calcium phosphate, which replaces the traditional alkali for adjusting pH value. It will not introduce impure metals, reduces production costs, and improves economic benefits. More importantly, it can recycle calcium phosphate solid waste and recover the valuable metal lithium in calcium phosphate.
在实际操作过程中，除铁铝是向除铜后液中加入磷酸钙，固液分离后得到铁铝渣和除铁铝后液；在除铁铝的过程中，控制磷酸钙的加入量与除铜后液中铁铝总量的摩尔比为0.8-1.1:1(如0.8:1、0.9:1、1.0:1、1.1:1等)，通过精确控制磷酸钙的加入量能够使铁铝充分地沉积出来，还避免了过多磷元素的引入，不会造成中间产品磷杂质含量过高的问题。In the actual operation process, iron and aluminum are removed by adding calcium phosphate to the copper removal liquid, and iron-aluminum slag and iron-aluminum removal liquid are obtained after solid-liquid separation; in the process of iron and aluminum removal, the molar ratio of the amount of calcium phosphate added to the total amount of iron and aluminum in the copper removal liquid is controlled to be 0.8-1.1:1 (such as 0.8:1, 0.9:1, 1.0:1, 1.1:1, etc.). By precisely controlling the amount of calcium phosphate added, the iron and aluminum can be fully deposited, and the introduction of too much phosphorus element is avoided, which will not cause the problem of excessive phosphorus impurity content in the intermediate product.
进一步地，除铁铝包括：将除铜后液加热至80-95℃，加入氧化剂和磷酸钙，反应20-60min，固液分离，利用氧化剂将溶液中的二价铁离子氧化，和磷酸钙反应后沉积下来，钙离子和溶液中的硫酸根离子结合沉积下来。Furthermore, the iron and aluminum removal includes: heating the copper-removed solution to 80-95°C, adding an oxidant and calcium phosphate, reacting for 20-60 minutes, separating the solid and the liquid, oxidizing the divalent iron ions in the solution with the oxidant, reacting with the calcium phosphate and depositing them, and the calcium ions combine with the sulfate ions in the solution and deposit them.
具体地，加热温度可以为80℃、85℃、90℃、95℃等，反应时间可以为20min、30min、40min、50min、60min等。Specifically, the heating temperature can be 80°C, 85°C, 90°C, 95°C, etc., and the reaction time can be 20 min, 30 min, 40 min, 50 min, 60 min, etc.
在一些实施例中，氧化剂选自氯酸钠、氯酸钾、二氧化锰和过氧化氢中的至少一种，氧化剂加入的摩尔量是氧化除铜后液中亚铁理论量的1～1.5倍。氧化剂可以选择以上原料中的任意一种或几种，通过控制氧化剂用量以促进铁铝的充分沉积。In some embodiments, the oxidant is selected from at least one of sodium chlorate, potassium chlorate, manganese dioxide and hydrogen peroxide, and the molar amount of the oxidant added is 1 to 1.5 times the theoretical amount of ferrous iron in the solution after copper removal by oxidation. The oxidant can be selected from any one or more of the above raw materials, and the amount of the oxidant is controlled to promote the sufficient deposition of iron and aluminum.
在一些实施例中，磷酸钙加入时控制液固比为0-10，也就是说磷酸钙可以以磷酸钙溶液的形式加入，也可以以干粉的形式加入，这种形式减少了水的引入，节约了水资源，加快了反应进程，提高了生产效率。以溶液形式加入时液固质量比可以为1:1、2:1、3:1、4:1、5:1、6:1、7:1、8:1、9:1、10:1等。In some embodiments, when calcium phosphate is added, the liquid-to-solid ratio is controlled to be 0-10, that is, calcium phosphate can be added in the form of calcium phosphate solution or in the form of dry powder, which reduces the introduction of water, saves water resources, speeds up the reaction process, and improves production efficiency. When added in the form of solution, the liquid-to-solid mass ratio can be 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, etc.
在一些实施例中，对得到的铁铝渣进行洗涤，以去除表面杂质，洗涤时控制液固质量比为3-10:1，如可以为3:1、4:1、5:1、6:1、7:1、8:1、9:1、10:1等。In some embodiments, the obtained iron-aluminum slag is washed to remove surface impurities, and the liquid-to-solid mass ratio during washing is controlled to be 3-10:1, such as 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, etc.
经检测：除铁铝后液pH值为2.0-5.0，铁铝渣Ni、Co、Mn、Li有价金属含量不高于0.01％，除铁铝后液P含量＜0.1g/L。除铁铝后液磷含量低，降低了水处理的成本；降低铁铝渣中有价金属的夹带量，降低了有价金属的损失率，提高了生产经济效益，降低了有害金属对环境 的污染。After testing, the pH value of the liquid after iron and aluminum removal is 2.0-5.0, the content of Ni, Co, Mn, and Li in the iron and aluminum slag is not higher than 0.01%, and the P content of the liquid after iron and aluminum removal is less than 0.1g/L. The low phosphorus content of the liquid after iron and aluminum removal reduces the cost of water treatment; reduces the amount of valuable metals entrained in the iron and aluminum slag, reduces the loss rate of valuable metals, improves production economic benefits, and reduces the environmental impact of harmful metals pollution.
S3、沉镍钴锰S3, nickel, cobalt and manganese precipitation
向除铁铝后液中加入碱溶液，固液分离后得到氢氧化镍钴锰和沉镍钴锰后液，以回收浸出液中的镍钴锰等有价金属。Alkaline solution is added to the liquid after iron and aluminum removal, and nickel, cobalt and manganese hydroxide and nickel, cobalt and manganese precipitation liquid are obtained after solid-liquid separation to recover valuable metals such as nickel, cobalt and manganese in the leaching solution.
在实际操作过程中，沉镍钴锰的过程包括：将除铁铝后液加热至50-95℃，加入碱溶液反应0.5-3h，固液分离；加入的碱溶液的量是控制氢氧根和镍钴锰总量的摩尔比为2.05～2.5：1(如2.05:1、2.10:1、2.20:1、2.30:1、2.40:1、2.50:1等)，以使镍钴锰元素能够充分地沉积下来。In actual operation, the process of precipitating nickel, cobalt and manganese includes: heating the liquid after iron and aluminum removal to 50-95°C, adding alkaline solution to react for 0.5-3h, and separating the solid and liquid; the amount of alkaline solution added is to control the molar ratio of hydroxide to the total amount of nickel, cobalt and manganese to be 2.05-2.5:1 (such as 2.05:1, 2.10:1, 2.20:1, 2.30:1, 2.40:1, 2.50:1, etc.), so that the nickel, cobalt and manganese elements can be fully deposited.
具体地，除铁铝后液的加热温度可以为50℃、60℃、70℃、80℃、90℃、95℃等，反应时间可以为0.5h、1.0h、1.5h、2.0h、2.5h、3.0h等。Specifically, the heating temperature of the liquid after iron and aluminum removal can be 50°C, 60°C, 70°C, 80°C, 90°C, 95°C, etc., and the reaction time can be 0.5h, 1.0h, 1.5h, 2.0h, 2.5h, 3.0h, etc.
优选地，沉镍钴锰的过程中加入的碱溶液选自氢氧化钠溶液、氢氧化钾溶液和氨水中的至少一种，采用以上几种碱液均可。碱溶液的质量分数为25-35％，如25％、30％、35％等。Preferably, the alkaline solution added during the precipitation of nickel, cobalt and manganese is selected from at least one of sodium hydroxide solution, potassium hydroxide solution and ammonia water, and any of the above alkaline solutions can be used. The mass fraction of the alkaline solution is 25-35%, such as 25%, 30%, 35%, etc.
S4、一次沉锂S4, primary lithium precipitation
向沉镍钴锰后液中加入碳酸盐，固液分离后得到碳酸锂和一次沉锂后液，沉镍钴锰后液中的锂大部分能够以碳酸锂的形式沉积出来，将高价锂元素得到回收。Carbonate is added to the liquid after nickel, cobalt and manganese precipitation, and lithium carbonate and a liquid after primary lithium precipitation are obtained after solid-liquid separation. Most of the lithium in the liquid after nickel, cobalt and manganese precipitation can be precipitated in the form of lithium carbonate, and the high-priced lithium element is recovered.
在一些实施例中，一次沉锂的过程包括：将沉镍钴锰后液加热至80-95℃，加入碳酸盐溶液反应0.5-3h，固液分离；其中，碳酸盐的加入量是控制碳酸根离子的量与沉镍钴锰后液中锂离子含量的摩尔比为0.5～5：1(如0.5:1、1.0:1、2.0:1、3.0:1、4.0:1、5.0:1等)。通过精确控制反应条件以使锂能够更充分地沉积出来。In some embodiments, the process of primary lithium precipitation includes: heating the solution after nickel, cobalt and manganese precipitation to 80-95°C, adding carbonate solution to react for 0.5-3h, and separating the solid and liquid; wherein the amount of carbonate added is to control the molar ratio of the amount of carbonate ions to the content of lithium ions in the solution after nickel, cobalt and manganese precipitation to be 0.5-5:1 (such as 0.5:1, 1.0:1, 2.0:1, 3.0:1, 4.0:1, 5.0:1, etc.). The reaction conditions are precisely controlled to allow lithium to be deposited more fully.
具体地，沉镍钴锰后液的加热温度可以为80℃、85℃、90℃、95℃等，反应时间可以为0.5h、1.0h、2.0h、3.0h等。Specifically, the heating temperature of the solution after nickel, cobalt and manganese precipitation can be 80°C, 85°C, 90°C, 95°C, etc., and the reaction time can be 0.5h, 1.0h, 2.0h, 3.0h, etc.
在一些实施例中，碳酸盐选自碳酸钠、碳酸钾和碳酸铵中的至少一种，可以为以上任意一种。碳酸盐溶液的质量分数为10-20％，如可以为10％、15％、20％等。In some embodiments, the carbonate is selected from at least one of sodium carbonate, potassium carbonate and ammonium carbonate, and may be any of the above. The mass fraction of the carbonate solution is 10-20%, such as 10%, 15%, 20%, etc.
S5、二次沉锂S5, secondary lithium deposition
向一次沉锂后液中加入磷酸盐，固液分离后得到磷酸锂和二次沉锂后液，通过二次沉锂将一次沉锂过程没有沉积下来的锂进一步从溶液中去除得到回收。Phosphate is added to the liquid after the first lithium precipitation, and lithium phosphate and the liquid after the second lithium precipitation are obtained after solid-liquid separation. The lithium that is not deposited in the first lithium precipitation process is further removed from the solution through the second lithium precipitation and recovered.
在一些实施例中，二次沉锂的过程包括：向一次沉锂后液中加入磷酸盐溶液反应0.5-3h，固液分离，控制反应温度为20-80℃；其中，磷酸盐的加入量是控制磷酸根离子的量与一次沉锂后液中锂离子含量的摩尔比为0.3～5：1(如0.3:1、1.0:1、2.0:1、3.0:1、4.0:1、5.0:1等)。通过控制二次沉锂的反应条件，有利于将溶液中残留的锂充分去除，得到充分回收。 In some embodiments, the process of secondary lithium precipitation includes: adding phosphate solution to the liquid after primary lithium precipitation for reaction for 0.5-3h, solid-liquid separation, and controlling the reaction temperature to 20-80°C; wherein, the amount of phosphate added is to control the molar ratio of the amount of phosphate ions to the content of lithium ions in the liquid after primary lithium precipitation to be 0.3-5:1 (such as 0.3:1, 1.0:1, 2.0:1, 3.0:1, 4.0:1, 5.0:1, etc.). By controlling the reaction conditions of secondary lithium precipitation, it is beneficial to fully remove the residual lithium in the solution and obtain full recovery.
具体地，反应温度可以为20℃、30℃、40℃、50℃、60℃、70℃、80℃等，反应时间可以为0.5h、1.0h、2.0h、3.0h等。Specifically, the reaction temperature can be 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, etc., and the reaction time can be 0.5h, 1.0h, 2.0h, 3.0h, etc.
在一些实施例中，磷酸盐选自磷酸钠、磷酸钾、磷酸铵、磷酸氢铵和磷酸二氢铵中的至少一种，可以为以上几种磷酸盐中的任意一种或几种。磷酸盐溶液的质量分数为10-20％，如可以为10％、15％、20％等。In some embodiments, the phosphate is selected from at least one of sodium phosphate, potassium phosphate, ammonium phosphate, ammonium hydrogen phosphate and ammonium dihydrogen phosphate, and can be any one or more of the above phosphates. The mass fraction of the phosphate solution is 10-20%, such as 10%, 15%, 20%, etc.
S6、除磷；S6, phosphorus removal;
除磷是在二次沉锂后液中加入过量的钙盐，固液分离后得到磷酸钙和合格废水，沉积下来的磷酸钙呈碱性，能够用于除铁铝的过程中。Phosphorus removal is done by adding excess calcium salt to the liquid after secondary lithium precipitation, and obtaining calcium phosphate and qualified wastewater after solid-liquid separation. The precipitated calcium phosphate is alkaline and can be used in the process of iron and aluminum removal.
在一些实施例中，除磷的过程包括：向二次沉锂后液中加入过量的钙盐反应0.5-3h，固液分离，控制反应温度为20-80℃；其中，钙盐的加入量是控制钙与二次沉锂后液中磷酸根的摩尔比为0.6～5：1(如0.6:1、1.0:1、2.0:1、3.0:1、4.0:1、5.0:1等)。通过控制除磷过程的操作参数，以使磷得到更充分的去除，使废水满足排放标准。In some embodiments, the phosphorus removal process includes: adding an excess of calcium salt to the secondary lithium precipitation solution for a reaction of 0.5-3 hours, solid-liquid separation, and controlling the reaction temperature to 20-80°C; wherein the amount of calcium salt added is to control the molar ratio of calcium to phosphate in the secondary lithium precipitation solution to be 0.6-5:1 (such as 0.6:1, 1.0:1, 2.0:1, 3.0:1, 4.0:1, 5.0:1, etc.). By controlling the operating parameters of the phosphorus removal process, phosphorus can be more fully removed and the wastewater can meet the discharge standards.
具体地，反应温度可以为20℃、30℃、40℃、50℃、60℃、70℃、80℃等，反应时间可以为0.5h、1.0h、2.0h、3.0h等。Specifically, the reaction temperature can be 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, etc., and the reaction time can be 0.5h, 1.0h, 2.0h, 3.0h, etc.
在一些实施例中，钙盐选自氧化钙、氢氧化钙和硫酸钙中的至少一种，可以选择以上任意一种或几种。钙盐以浆料的形式加入为宜，钙盐的质量分数为10-20％，如可以为10％、15％、20％等。In some embodiments, the calcium salt is selected from at least one of calcium oxide, calcium hydroxide and calcium sulfate, and any one or more of the above can be selected. The calcium salt is preferably added in the form of slurry, and the mass fraction of the calcium salt is 10-20%, such as 10%, 15%, 20%, etc.
以下结合实施例对本发明的特征和性能作进一步的详细描述。The features and performance of the present invention are further described in detail below in conjunction with the embodiments.
需要说明的是，以下实施例中废旧锂电池浸出液的制备过程如下：It should be noted that the preparation process of the waste lithium battery leachate in the following examples is as follows:
废旧锂电池料经焙烧，焙烧后的物料，经破碎、分选得到电池粉，然后加硫酸浸出，得到电池浸出液。The waste lithium battery material is roasted, and the roasted material is crushed and sorted to obtain battery powder, which is then leached with sulfuric acid to obtain battery leachate.
经检测废旧锂电池浸出液的组成如表1所示：The composition of the waste lithium battery leachate is shown in Table 1:
表1废旧锂电池浸出液元素检测(g/L)
Table 1 Element detection of waste lithium battery leachate (g/L)
实施例1Example 1
本实施例提供一种废旧锂电池浸出液的处理方法，包括如下步骤：This embodiment provides a method for treating waste lithium battery leachate, comprising the following steps:
(1)取废旧锂电池浸出液1L，加热至80℃，加入5.66g的Mn粉，反应1h，过滤的得到单质铜和除铜后液；(1) Take 1 L of waste lithium battery leachate, heat it to 80°C, add 5.66 g of Mn powder, react for 1 hour, and filter to obtain elemental copper and copper-removed liquid;
(2)步骤(1)得到除铜后液加热至90℃，加入0.06g氧化剂氯酸钠和上一浸出液处理 循环工艺步骤(6)得到的磷酸钙，充分搅拌，按Fe、Al总摩尔量与磷酸钙的摩尔量比为1：0.8加入磷酸钙，反应30min后，过滤，得到铁铝渣和除铁铝后液；(2) The copper-removed solution obtained in step (1) is heated to 90°C, 0.06 g of oxidizing agent sodium chlorate is added and treated with the above leaching solution. The calcium phosphate obtained in the recycling process step (6) is fully stirred, and calcium phosphate is added at a molar ratio of the total molar amount of Fe and Al to the molar amount of calcium phosphate of 1:0.8. After reacting for 30 minutes, it is filtered to obtain iron-aluminum slag and iron-aluminum-removed liquid;
(3)步骤(2)得到的除铁铝后液加热至60℃，加入质量分数为30％的氢氧化钠溶液0.42L，反应2h，过滤得到氢氧化镍钴锰和沉镍钴锰后液；(3) The iron and aluminum-removed liquid obtained in step (2) is heated to 60° C., 0.42 L of a 30% sodium hydroxide solution is added, the mixture is reacted for 2 h, and the nickel, cobalt and manganese hydroxides and the nickel, cobalt and manganese precipitation liquid are obtained by filtration;
(4)步骤(3)得到的沉镍钴锰后液加热至90℃，加入质量分数15％的碳酸钠溶液0.63L，反应2h，过滤得到碳酸锂和一次沉锂后液；(4) The nickel-cobalt-manganese precipitation solution obtained in step (3) is heated to 90° C., 0.63 L of a 15% by mass sodium carbonate solution is added, the reaction is carried out for 2 h, and lithium carbonate and a primary lithium precipitation solution are obtained by filtering;
(5)取步骤(4)得到的一次沉锂后液，加入质量分数15％的磷酸钠溶液0.26L，常温(25℃)下反应2h，过滤得到磷酸锂和二次沉锂后液；(5) taking the primary lithium precipitation liquid obtained in step (4), adding 0.26 L of 15% sodium phosphate solution by mass, reacting at room temperature (25° C.) for 2 h, and filtering to obtain lithium phosphate and secondary lithium precipitation liquid;
(6)取步骤(5)得到的二次沉锂后液，加入质量分数为15％氧化钙浆料0.058L，常温(25℃)下反应2h，过滤得到磷酸钙和合格废水。(6) Take the secondary lithium precipitation liquid obtained in step (5), add 0.058L of calcium oxide slurry with a mass fraction of 15%, react at room temperature (25°C) for 2h, and filter to obtain calcium phosphate and qualified wastewater.
实施例2-8Embodiment 2-8
与实施例1的区别仅在于：步骤(2)磷酸钙的加入量不同。实施例2-8中Fe、Al总摩尔量与磷酸钙的摩尔量比依次为1:1.1、1:0.85、1:0.9、1:1.0、1:1.05、1:1.3、1:0.5。The only difference from Example 1 is that the amount of calcium phosphate added in step (2) is different. The molar ratio of the total molar amount of Fe and Al to the molar amount of calcium phosphate in Examples 2-8 is 1:1.1, 1:0.85, 1:0.9, 1:1.0, 1:1.05, 1:1.3, and 1:0.5, respectively.
需要补充的是，以上实施例仅是发明人尝试过的众多实施例的举例，关于反应温度、时间等参数在本申请所限定的范围内即可保证处理效果，达到与实施例1类似的效果。It should be added that the above embodiments are only examples of many embodiments tried by the inventors. The processing effect can be guaranteed within the range specified in this application for parameters such as reaction temperature and time, achieving an effect similar to that of Example 1.
实施例9-12Examples 9-12
与实施例1的区别仅在于：步骤(2)除铁铝的反应温度不同。实施例9～12反应温度分别为，40℃、80℃、85℃、95℃。The only difference from Example 1 is that the reaction temperature of step (2) for removing iron and aluminum is different. The reaction temperatures of Examples 9 to 12 are 40°C, 80°C, 85°C, and 95°C, respectively.
需要补充的是，以上实施例仅是发明人尝试过的众多实施例的举例，关于其他参数在本申请所限定的范围内即可保证处理效果，达到与实施例1类似的效果。It should be added that the above embodiments are only examples of many embodiments tried by the inventors, and the processing effect can be guaranteed as long as other parameters are within the range specified in this application, achieving an effect similar to that of Embodiment 1.
对比例1Comparative Example 1
对比例1的具体方法参照中国专利CN201811398512.2。The specific method of comparative example 1 refers to Chinese patent CN201811398512.2.
经检测：铁铝渣干基Ni：0.5～1.4wt％，Co:0.06～0.5wt％，Mn:0～0.05wt％，镍钴含量均较高，造成了有价金属的浪费。After testing: the dry basis Ni of the iron-aluminum slag is 0.5-1.4wt%, Co is 0.06-0.5wt%, and Mn is 0-0.05wt%. The nickel and cobalt contents are both relatively high, resulting in a waste of valuable metals.
试验例1Test Example 1
测试实施例1-8中的处理方法的效果，分别测试除铁铝后液参数、铁铝渣参数以及锂回收率，结果如表2所示。The effects of the treatment methods in Examples 1-8 were tested, and the liquid parameters after iron and aluminum removal, iron and aluminum slag parameters, and lithium recovery rate were tested respectively. The results are shown in Table 2.
表2实施例1-8中的处理方法的处理效果测试结果

Table 2 Treatment effect test results of the treatment methods in Examples 1-8

从表2可以看出，实施例1-6锂的回收率均较高(锂回收率大于99％)，且除铁铝后液中磷等杂质的含量非常少，铁铝渣中镍钴锰锂含量非常少。但是，实施例7-8中磷酸钙与溶液中铁铝摩尔比超出0.8-1.1:1，除铁铝后液和铁铝渣中杂质含量均非常高，为后续处理增加了难度。As can be seen from Table 2, the lithium recovery rates of Examples 1-6 are all relatively high (lithium recovery rate is greater than 99%), and the content of impurities such as phosphorus in the solution after iron and aluminum removal is very low, and the content of nickel, cobalt, manganese and lithium in the iron-aluminum slag is very low. However, in Examples 7-8, the molar ratio of calcium phosphate to iron and aluminum in the solution exceeds 0.8-1.1:1, and the impurity content in the solution after iron and aluminum removal and the iron-aluminum slag is very high, which increases the difficulty of subsequent treatment.
试验例2Test Example 2
测试实施例1和实施例9-12中的步骤(2)的过滤效果，结果如表3。The filtering effect of step (2) in Example 1 and Examples 9-12 was tested. The results are shown in Table 3.
表3过滤速度测试结果
Table 3 Filtration speed test results
从表3可以看出，当温度大于80℃时，过滤效果很好，并且温度越高，过滤效果越好。因此反应温度在80～95℃时，物料有较好的固液分离速度，从而提高生产效率，降低生产成本。It can be seen from Table 3 that when the temperature is greater than 80°C, the filtration effect is very good, and the higher the temperature, the better the filtration effect. Therefore, when the reaction temperature is between 80 and 95°C, the material has a better solid-liquid separation rate, thereby improving production efficiency and reducing production costs.
以上仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。 The above are only preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims (10)

  1. 一种废旧锂电池浸出液的处理方法，其特征在于，包括依次进行的除铜、除铁铝、沉镍钴锰、一次沉锂、二次沉锂和除磷；A method for treating waste lithium battery leachate, characterized in that it comprises the following steps of removing copper, removing iron and aluminum, precipitating nickel, cobalt and manganese, primary lithium precipitation, secondary lithium precipitation and removing phosphorus in sequence;
    其中，所述除磷是在二次沉锂后液中加入过量的钙盐，固液分离后得到磷酸钙和废水，所述除铁铝是利用所述磷酸钙进行处理。Among them, the phosphorus removal is to add excess calcium salt to the liquid after the secondary lithium precipitation, and obtain calcium phosphate and wastewater after solid-liquid separation. The iron and aluminum removal is carried out by using the calcium phosphate.
  2. 根据权利要求1所述的处理方法，其特征在于，包括：The processing method according to claim 1, characterized in that it comprises:
    除铜：向废旧锂电池浸出液中加入金属单质进行置换，固液分离后得到单质铜和除铜后液；Copper removal: adding metal elements to the waste lithium battery leachate for replacement, and obtaining elemental copper and copper-removed liquid after solid-liquid separation;
    除铁铝：向所述除铜后液中加入所述磷酸钙，固液分离后得到铁铝渣和除铁铝后液；在除铁铝的过程中，控制所述磷酸钙的加入量与所述除铜后液中铁铝总量的摩尔比为0.8-1.1:1；Iron and aluminum removal: adding the calcium phosphate to the copper removal liquid, and obtaining iron and aluminum slag and iron and aluminum removal liquid after solid-liquid separation; in the process of iron and aluminum removal, controlling the molar ratio of the amount of the calcium phosphate added to the total amount of iron and aluminum in the copper removal liquid to be 0.8-1.1:1;
    沉镍钴锰：向所述除铁铝后液中加入碱溶液，固液分离后得到氢氧化镍钴锰和沉镍钴锰后液；Precipitating nickel, cobalt and manganese: adding an alkaline solution to the liquid after iron and aluminum removal, and obtaining nickel, cobalt and manganese hydroxide and a liquid after nickel, cobalt and manganese precipitation after solid-liquid separation;
    一次沉锂：向所述沉镍钴锰后液中加入碳酸盐，固液分离后得到碳酸锂和一次沉锂后液；Primary lithium precipitation: adding carbonate to the solution after nickel, cobalt and manganese precipitation, and obtaining lithium carbonate and the solution after primary lithium precipitation after solid-liquid separation;
    二次沉锂：向所述一次沉锂后液中加入磷酸盐，固液分离后得到磷酸锂和二次沉锂后液；Secondary lithium precipitation: adding phosphate to the liquid after the primary lithium precipitation, and obtaining lithium phosphate and the liquid after the secondary lithium precipitation after solid-liquid separation;
    除磷：向所述二次沉锂后液中加入过量的钙盐，固液分离后得到磷酸钙和合格废水。Phosphorus removal: adding an excess of calcium salt to the liquid after the secondary lithium precipitation, and obtaining calcium phosphate and qualified wastewater after solid-liquid separation.
  3. 根据权利要求2所述的处理方法，其特征在于，所述金属单质选自锰粉、铁粉和铝粉中的至少一种，置换反应时间为0.5-3h，反应温度为60-90℃；The treatment method according to claim 2, characterized in that the metal element is selected from at least one of manganese powder, iron powder and aluminum powder, the replacement reaction time is 0.5-3h, and the reaction temperature is 60-90°C;
    优选地，所述金属单质的加入量与所述废旧锂电池浸出液中铜含量的摩尔比为1.05～1.2：1。Preferably, the molar ratio of the added amount of the metal element to the copper content in the waste lithium battery leachate is 1.05-1.2:1.
  4. 根据权利要求2所述的处理方法，其特征在于，所述除铁铝包括：将所述除铜后液加热至80-95℃，加入氧化剂和所述磷酸钙，反应20-60min，固液分离；The treatment method according to claim 2 is characterized in that the iron and aluminum removal comprises: heating the copper-removed liquid to 80-95° C., adding an oxidant and the calcium phosphate, reacting for 20-60 minutes, and separating the solid and liquid;
    优选地，磷酸钙加入时控制液固比为0-10；Preferably, when calcium phosphate is added, the liquid-to-solid ratio is controlled to be 0-10;
    优选地，对得到的铁铝渣进行洗涤，洗涤时控制液固质量比为3-10:1。Preferably, the obtained iron-aluminum slag is washed, and the liquid-to-solid mass ratio is controlled to be 3-10:1 during washing.
  5. 根据权利要求4所述的处理方法，其特征在于，所述氧化剂选自氯酸钠、氯酸钾、二氧化锰和过氧化氢中的至少一种，所述氧化剂加入的摩尔量是氧化所述除铜后液中亚铁理论量的1～1.5倍。The treatment method according to claim 4 is characterized in that the oxidant is selected from at least one of sodium chlorate, potassium chlorate, manganese dioxide and hydrogen peroxide, and the molar amount of the oxidant added is 1 to 1.5 times the theoretical amount of ferrous iron in the copper removal solution.
  6. 根据权利要求2所述的处理方法，其特征在于，所述沉镍钴锰的过程包括：将所述除铁铝后液加热至50-95℃，加入碱溶液反应0.5-3h，固液分离；加入的所述碱溶液的量是控制氢氧根和镍钴锰总量的摩尔比为2.05～2.5：1； The treatment method according to claim 2 is characterized in that the process of precipitating nickel, cobalt and manganese comprises: heating the liquid after iron and aluminum removal to 50-95° C., adding an alkaline solution to react for 0.5-3 hours, and separating the solid and liquid; the amount of the alkaline solution added is to control the molar ratio of hydroxide to the total amount of nickel, cobalt and manganese to be 2.05-2.5:1;
    优选地，所述沉镍钴锰的过程中加入的碱溶液选自氢氧化钠溶液、氢氧化钾溶液和氨水中的至少一种，所述碱溶液的质量分数为25-35％。Preferably, the alkaline solution added during the nickel, cobalt and manganese precipitation process is selected from at least one of sodium hydroxide solution, potassium hydroxide solution and ammonia water, and the mass fraction of the alkaline solution is 25-35%.
  7. 根据权利要求2所述的处理方法，其特征在于，所述一次沉锂的过程包括：将所述沉镍钴锰后液加热至80-95℃，加入碳酸盐溶液反应0.5-3h，固液分离；The treatment method according to claim 2 is characterized in that the process of the primary lithium precipitation comprises: heating the solution after the nickel, cobalt and manganese precipitation to 80-95° C., adding a carbonate solution to react for 0.5-3 hours, and separating the solid from the liquid;
    其中，碳酸盐的加入量是控制碳酸根离子的量与所述沉镍钴锰后液中锂离子含量的摩尔比为0.5～5：1；The amount of carbonate added is to control the molar ratio of carbonate ions to the lithium ion content in the solution after nickel, cobalt and manganese precipitation to be 0.5 to 5:1;
    优选地，所述碳酸盐选自碳酸钠、碳酸钾和碳酸铵中的至少一种，所述碳酸盐溶液的质量分数为10-20％。Preferably, the carbonate is selected from at least one of sodium carbonate, potassium carbonate and ammonium carbonate, and the mass fraction of the carbonate solution is 10-20%.
  8. 根据权利要求2所述的处理方法，其特征在于，所述二次沉锂的过程包括：向所述一次沉锂后液中加入磷酸盐溶液反应0.5-3h，固液分离，控制反应温度为20-80℃；The treatment method according to claim 2 is characterized in that the secondary lithium precipitation process comprises: adding a phosphate solution to the liquid after the primary lithium precipitation for a reaction of 0.5-3h, solid-liquid separation, and controlling the reaction temperature to 20-80°C;
    其中，磷酸盐的加入量是控制磷酸根离子的量与所述一次沉锂后液中锂离子含量的摩尔比为0.3～5：1；The amount of phosphate added is to control the molar ratio of the amount of phosphate ions to the content of lithium ions in the solution after the primary lithium precipitation to be 0.3 to 5:1;
    优选地，所述磷酸盐选自磷酸钠、磷酸钾、磷酸铵、磷酸氢铵和磷酸二氢铵中的至少一种，所述磷酸盐溶液的质量分数为10-20％。Preferably, the phosphate is selected from at least one of sodium phosphate, potassium phosphate, ammonium phosphate, ammonium hydrogen phosphate and diammonium phosphate, and the mass fraction of the phosphate solution is 10-20%.
  9. 根据权利要求2所述的处理方法，其特征在于，所述除磷的过程包括：向所述二次沉锂后液中加入过量的钙盐反应0.5-3h，固液分离，控制反应温度为20-80℃；The treatment method according to claim 2 is characterized in that the phosphorus removal process comprises: adding excess calcium salt to the secondary lithium precipitation liquid for a reaction of 0.5-3h, solid-liquid separation, and controlling the reaction temperature to 20-80°C;
    其中，所述钙盐的加入量是控制钙与所述二次沉锂后液中磷酸根的摩尔比为0.6～5：1。The amount of calcium salt added is to control the molar ratio of calcium to phosphate in the secondary lithium precipitation solution to be 0.6 to 5:1.
  10. 根据权利要求9所述的处理方法，其特征在于，所述钙盐选自氧化钙、氢氧化钙和硫酸钙中的至少一种；The treatment method according to claim 9, characterized in that the calcium salt is selected from at least one of calcium oxide, calcium hydroxide and calcium sulfate;
    优选地，所述钙盐以浆料的形式加入，钙盐的质量分数为10-20％。 Preferably, the calcium salt is added in the form of slurry, and the mass fraction of the calcium salt is 10-20%.
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